Ice color



Patented Mart 19, 1940 UNITED STATES PATENT OFFICE i v 'ICE COLOR a Frithj'of Zw ilgnieyer, Arden, Del., assignor to E I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application July 2,1937,

Serial No. 151,670

14 claims. (01. 260-188) I Y Y in which Aryl is an, aromatic nucleus of a compound from the group 1 consisting of benzene, 2o naphthalene, vcarbazole, anthracene, diphenyl and azo-benzene compounds, one X is hydroxy and the other'is hydrogen, one Y is amino and the other Ys are hydrogen, and n is an integer 1 or 2, depending upon whether the Aryl-azo that is Aryl may be unsubstituted or it may be substituted generally ,by groups which do not 30 lend solubility to the compounds. l It is an object of the invention to provide new azo combinations by means of which cotton, re-

generated cellulose and similar materials can be dyed easily, in shades of brown which have good fa'stness to washing, light and the exposures to 3 which fibres and textile materials'are subjected.

Another object of the invention is to provide fabrics dyed with the new compounds. Another object of the inventionis to provide processes for making the new combinations and process for 40 dyeing in shades of brown which have superior properties and are more convenient to operate than processes for obtaimng such dyemgsas I not limited to the examples practiced heretofore. Other objects of the invention will be apparent from the following de- 45 scription.

The objects of the invention are attained generally by diazotizing an amino-azo compound which is represented by the following formula acetic acid; The goods werethen' submerged in in which Aryl is the aryl radical ofa compound y from the group consisting of benzene, naphthalene, carbazole, anthra'cene, diphenyl and ambenzene compounds, which may be substituted by anyn-auxoc'hrome but not bysulfonic acid; 5

or carboxyhone X -is hydroxy and the other is hydrogen, n is aninteger 1 or 2, and NH2 is substituted'iii anyone of, the positions of the benzene ring of fthenaphthalene nucleus which is not substituted-"by the azo'group. .This' ,diazotized compound is then coupled to a diazo dye coupling component which is free from solu-' bilizing groups, such as one from the group consisting of the aryl-amides or ortho-hydroxyaryl-carboxylic acid and the aryl amides of beta-keto-carboxylic acid, In the dyeing of l fabrics the fabric may desirably be impregnated these diaaoi i hino compounds or anti-diazotates are mixed with the described'coupling compo nents, themateri'al to be dyed is dyed with the mixtureand the" color is developedby treatment with weak acids. In printing, a suitable m'ixture containing the diazoimino or anti-diazotate and the coupling component is made, printed on thematerial to be dyed andvthen developed. The

aryl-amides of .theformula may also be con- "verted to stabilized diazo salts and these may be 5 used for dyeing and printing on fibres which were previously impregnated with the coupling components.

'The invention will be more fully understood by reference to the following examples in which 40 all quantities are expressed in parts by weight unless otherwise specified, but the invention is nated by immersing in a bath heated to about 70 C. and-containing 2 grams of 2-('2'-hydroxynaphthalene-3'-carboyl-amino) -1-methoxy benzene, 2 cubic centimeters of alcohol and 2, cubic centimeters of 30% caustic soda solution. The goods were squeezed and submerged in a diazo solution containing 2 granrlsflof diazotizedf8- -diinethyl behzene-azo) -amino 7 hy droxy-naphthalene which was slightly acid with a 2% caustic soda solution, rinsed, soaped 2 minutes at a boil, again rinsed and dried.

The goods was dyed a brown shade which was fast to light, washing and the usual exposures to which such fabrics are exposed.

The dye is represented by the following formula f It N=N con, HO@ H ONE-O Example 2 i bk N=N (FCH: How I: ONHQ Example 3 The procedure of Example 1 was repeated using a solution of diazotized 8-(4'-methyl-benzeneazo)-l-amino-7-hydroxy naphthalene instead of the diazo compound used therein.

A brown shade having similar properties to the dyeing of Example 1 was produced. The dye is represented by the following formula N 1% N=N O OH:

Example 4 10 grams of cotton piece goods were impregnated for 15 min. in a bath at about 70 C. containing 2 g. of 2-(2'-hydroxy-naphthalene-3'- carboyl-amino)-1-methyl-benzene, 2 cc. alcohol and 2 cc. 30% caustic soda. The cotton piece goods was squeezed and the dyeing was developed by submersion into one liter of a diazo solution containing 2 g. of diazotized 4-(2:5'-dichlor-benzene-azo) 1-amino 7 hydroxy-naphthalene, then into a second bath containing 1% caustic soda solution, rinsed, soaped 2 minutes at a boil, again rinsed and dried.

A deep, brown shade of good fastness was obtained. The dyestuff is represented by the following formula In an analogous manner, dyeings were produced from the following diazo and coupling components. These dyes had the improved properties of the dye described in Examples 1 to 4.

Diazo component Coupling component Color Brown.

8-(2-methyl-5-ch1oro-benzene-azo)-1-amino-7-hydtoxynaphthalene.

8-(2-methoxy-5-chlor-benzene-azo)-l-amino-7-hydroxynaphthalene.

8-(2-nitroy-chloro-benzene-azo)-1-amino-7-liydroxynaphthalene. o

8- l(flags-ntliraquinone-azo)-1-amlno-7-hydroxy-naphtlia- 8- l(gl-anthraquinone-azc)-1-amino-7l1ydroxy-naphthad0 81% -gnthraquinone-azo) -1-amlno-7-hydI0xy-naphtban 4:4-dl-(2-hydroxy-8-amino-naphthalene-1-azo)-3:3-

digiethyl-dlphenyl. o 8-4-(4"-dimethylamino-benzene-azo)-benzene-1-azo-1- amino-7-hydroxy-naphthalene. 4:4-di-(8-amino-2"-hydroxy-naphthalene-1-ezo)-3:3-

dimethly-diphenyleno-sulfone. 8-(3-azo-carbazole)-1-amino-7-hydroxy-naphthalene. 8-(2-metlioxy-5-chlor-benzene-azo)-1-amino-5-hydroxynaphthalene. 8-:?-d1chlor-benzene-azo)-1-amino-6-hydrow-napha one. 8-(2':5'-dlchlor-benzene-azo)-2-amino-7-hydroxy-nnphthalene.

2-(2-hydroxy-naphthalene-3'-carboyl-amino)-1-ethox benzene. 2-EJW-hydmXy-naphthaIene-W-carboyl-ammo)-1-methylenzene. 2-gz hydroxy-naphthalene-3-carboyl-amino)-i-ethoxyenzene. 2-(2-hydroxy-naphthalene-3-carboyl-amino)-l-methylbenzene. 2-(2-hydroxy-naphthalene-3'-carboyl-amino)-1-ethoxybenzene. Aceto-acetyl-para-phenetidine 2-(2-hydroxy-naphtha1ene-3-carboyl-amino)-l methylbenzene. Aceto-acetyl-para-phcnetldme 2-(2'-hydroxy-naphthalene-3-carboyl-amino)-1-mctl1ylbegzene. o

Yellowish brown. Brown.

Dark brown.

Brown.

Dark brown.

Brown. Do.

Black.

Yellowish brown.

Dark brown.

Brown.

Dia zo component I Coupling component Color 4-(3-nitro-benzene-azo)-l-actyl-amino-7-hydroxy-naph- Yellowish brown.

naphthalene. thelene. 26 8-(2-methoxy-fiwmethyl-benzene-azo)-1-amino-7-hy- 4-(4-nitro 2-methoxy-benzene-azo)-1-amino-7-hydroxy- D rk brown.

droxy-naphthalene." Y naphthalene. 27 8-(z inethoxy-benzene azo)-1-amino-7-hydroxy-naph- 4-ethoxy-a-chlor-acetwacet-anilide YellOWiSh o aene. 28 8-(benzenc-azo)-l=a1niho-7-hydr0xy-naphthalene Dlaceto-acet tolidine-sulfone The above examples illustrate only a few of the many new ice'colors obtainable from the new azo-arylamines described.

A very large number of coupling components which are devoid of solubilizing groups, namely sulfonic acid and carboxyl may be used. Most suitable are the arylamides of o-hydroxy-arylcarboxylic-acids and the arylamides beta-ketocarboxylic-acids. Among these are mentioned the ,arylamides' of Z-hydroxy-3-naphthoic-acid, of 2 hydroxy-anthracenee3,-carboxylic-acid, of 2- hydroxy-carbazole-3 carboxylic-acid, ,o-f fl-hydroxy-alpha-naphthocarbazole a 6' carbonylic acid, of 2-hydroXy-diphenylene-oxide-3carboxylic-acid. 'aceto-acetic-acid, of .benzoyl-aceticacid, ando-I' terephthaloyl-bis-acetic-acid.

The foregoing examples illustrate only a few of the many azo-arylamine compounds which are obtainable and can be used for the ice color bases to produce the compounds of the invention. The aryl nuclei-of these diazotizable compounds are free from watersolubilizing groups, namely carboxyl. and sulfonic acid groups. The group, Aryl as indicated in the general formulaof the diazotizable 'aryl amine compound may be the radical of a benzene, naphthalene, carbazole, anthracene, diphenyl or azoeben'zene nucleus which is free from a "solubilizing group and it-may beunsubstituted or substituted by an n-- auxochromasuch as alkyl, alkoxy, aryloxy, aral-- kyl, aralkoxy, aryl, hydro-aryloxy, acylamino,.

halogen, nitr'o and even others, except carboxy and sulfonic acid. In general from 1 to 3 sub-- stituents in Aryl are preferred, but more can be:

used." v

Among suitable amines other than those illus-- trated in the above examples which can be used.

4 to make the diazo base the following'are men-- tioned Ortho-toluidine Meta-toluidine 4-nitro-2-amino-anisole 4-chloro-2-amino-anisole 3-amino-benzo-trifluoride Ortho -phenetidine 4-b enzoyl-arnino-Z 5-diethoxy-aniline Alpha-naphthylamine l-amino-2- nethoxyenaphthalene 'Amino-azo-benzene Benzidine l 4 4 -diamino-diphenylamine 4 :4 -diamino-diphenyl- -ether 4 4' -diaminoazo-benzene 2 8-ainino -naphthols.

All the amino-naphthols may be utilized gen erany as second components in the preparation of the azo dye base. These amino-naphthols include"1:5-, 1:6 1:7 158-, 2:5-, 2:6-,'2:'1- and "The general methods of preparing'the azo dye base as well as numerous variations in thedetails of these 'methods are understood in the art. However, the coupling of the dlazotized aryle amines or tetrazotized arylene-di'amines must be carried out under "alkaline conditions in order 'to obtain products consisting chiefly of the compounds in which coupling has taken place in the nucleus of the amino-naphthol bearing the hydroxyl substituent.

'When the azo dye bases contain compounds which result from coupling to thenucleus of the amino-naphthol bearingthe amino substituent,

the products may be purified to free them from these impurities by various methods. The most products with a strong mineral acid under proper conditions of acidity, volume and temperature, the principles of which are generally understood by the art. The desired-products are caused to dissolve in the acid while the by-products are insoluble. The solutions are filtered and the purified products recovered from the filtrate by precipitation with alkali, filtration, washing and drying. Alternatively the-products may be puri- .:and similar related fibres by any of the procedures for producing ice colors and a large variety of shades can be produced by variations which I {are well known inthe art. The components of the dyes and the dyeings are economical to produce. I

The colors maybe applied by any of theprocesses for the application of ice colors. These are well known in the art but they 'find their most important use in printing according to which alkaline compositions containing the stabilized diazo component and the coupling components :is printed on the fibre and developed by hydroly- .sisof the diazo imi'rio compound. p

The following methods of imparting the colors to the fibres are mentioned.

1. The'fibres are padded with the arylamide :and then immersed ina solution of diazotized aryl amine.

conv'enient method consists in stirring the crude veloped by treatment with a mild acid, desirably at an elevated temperature.

4. The diazotized aryl amine is reacted with one of various aliphatic, isocyclic or heterocyclic amines which desirably contains a Water solubilizing group and a diazo imino derivative is formed. The fibre to be dyed is printed with a paste containing the diazo imino derivative and the arylamide. The color is then developed by hydrolyzing the diazo imino compound, such as by acting upon the printed goods with an acid, whereupon the coupling is immediately effected.

Among the desirable stabilizing agents are. methyl glucamine, diethanolamine, sarcosine, ethyl taurine, proline and 4-sulfo-2-amino-benzoic acid. The rate of color development will vary among the different derivates of the stabilizing agents but for a given stabilizing agent,

it has been found that the rapidity of development of the diazo imino compounds is rapid.

Since from the foregoing description of the invention it will be apparent to those skilled in the art that many embodiments of the invention may be made without departing from the spirit and scope thereof, it is to be understood that no limitations are intended except those which are specifically recited or are imposed by the prior art.

I claim:

1. A water-insoluble azo dyestuff represented by the formula in which Aryl is the radical of a group consisting of compounds of the benzene, the naphthalene, the carbazole, the anthracene, the diphenyl and the azo-benzene series which are devoid of solubilizing groups, one X is hydroxy and the other X is hydrogen, n is an integer not greater than 2, and R is the radical of an ice color coupling component, yielding when produced on the fiber various shades of good fastness properties.

2. A water-insoluble azo dyestufi represented by the formula Aryl N=N in which Aryl is the radical of a group consisting of compounds of the benzene, the naphthalene, the carbazole, the anthracene, the diphenyl and the azo-benzene series which are devoid of solubilizing groups, one X is hydroxy and the other X is hydrogen, n is an integer not greater than 2, and R is the residue of one of a group consisting of the arylamides of 2-3-hydroxy naphthoic acid which are connected to the azo bridge in the 1?- position and the arylainides of beta-lzeto-can boxylic acids, yielding when produced on the fiber various shades of good fastness properties. 3. A water-insoluble azo dyestufl represented by the formula in which Aryl is the radical of a group consisting orcompounds of the benzene, the naphthalene, the carbazole, the anthracene, the diphenyl and the azo-benzene series which are devoid of any solubilizinggroup, and R is the radical of an ice color coupling component, yielding when produced on the fiber various shades of good fastness properties.

4. A water-insoluble azo dyestufi represented by the formula It it I HO N= 1 011:

6. The compound represented by the formula:

Hac-

7. The compound represented by the formula:

8. Textile fiber dyed with .a dyestufi as claimed in claim 1.

9. Textile fiber dyed with a dyestufi as claimed in claim 2.

10. Textile fiber'dyed with a dyestuff as claimed 5 in claim 3.

11. Textile fiber dyed with a dyestufi as claimed in claim 4.

12. Textile fiber dyed with a dyestuff as claimed in claim 5. 1

13. Textile fiber dyed with a dyestuff as claimed in claim 6.

l4. Textile fiber dyed with a dyestuff as claimed in claim '7.

FRITHJ OF ZWILGMEYER. 15 

